Primary cell



I. C. BLAKE PRIMARY CELL.

Sept. 30, 1952 Filed April 24, 1951.

E D 5% u T E 8 0a J 6 l DEPOLARIZING 4- MIX ELECTROLYTE MgCl .6H 0+ Mg(NO8)2.6H2O In CH3 H MAGNESIUM -10 Patented Sept. 30, 1952 U T D A E PATENT omen;

PRIMARY CELL,

Ivan C. Blake, Freeport, Ill., assignor 'toBurgess Battery Company, Freeport, Ill.,'a corporation of. Delaware This invention relates to improvements in ourrentproducing primary cells and particularly to I that type of primary battery cell employing magnes'ium as the negative electrode.

The use of magnesium'as the negative electrode of current-producing primary "cells is attractive because of thegreater electrolytic activity of magnesium in comparison to that of the commonly used metal zinc, and the resulting higher voltage and greater energy delivering powers of the cells employing magnesium. However, magnesiumis also much more susceptible than zinc to spontaneous corrosion and its use in primary cells has for this reason been very severely limitedwbecause sati-sfa'ctory'shelf life is not obtained.

In the copending application of Joseph J. Coleman and Demetrios V. Louz'os, Serial No. 61,244,

filed November 20, 1948, a primary cell is disclosed having'magnesium as the negative" electrode and an electrolyte in which the solvent component is methanol and the solute component is from the group consisting of the chlorides, nitrates and perchlorates of magnesium and the metal-s 'elec tronegative to, magnesium. Such a cell possesses substantial current-delivering properties and shelfli-fe. w J

"In'accordance with the present invention, it":

has been discovered that :the use of a mixture of magnesium chloride and magnesium nitrate in the solute component of the electrolyte of a cell ofvthe character described in the mentioned ap--' plication results in unexpectedly greater -cur-.

rent-delivering power than "the 31156 of either magnesium chloride or magnesium nitrate alone,

and that the resulting cell possesses substantial shelf life. In accordance with the present in-- 'vention, water may be included with-methanol in.

th electrolyte solvent.

trode I6.

I t Application April24, 1951, Serial No. 222,707 7 4 Claims. (01. 136100) not limited to any particular physical arrangement but may :be incorporated-in any primary cell structure as may be desired.- The single cell illustrated is of flat wafer shape and is especially adapted for use in a multiple cell battery. The cell is made up of juxtaposed fiat elements consisting of,.in the order named, thenegative elec-' trode I0, the bibulous separating member l2, the depolarizing mix I4 and-"the positive elec- The bibulous' separator l2, in addition to coveringthe surface of the negative electrode l0 facing the mix I4,- preferablycovers the edges of the electrode l0 and the marginal portions of the opposite surface thereof. .The separator l2 and the mix I4 are liquid absorbent and are moistened with the liquid electrolyte which will be described in detail hereinafter;

The said elements are enclosed in an envelo-pe l8' of anon-conductive, liquideimpervious, electfolytte-rsistant sheet material, which maybe a flexible film of rubber hydrochloride, the copolymer of vinyl chloride and vinyl acetateya poly-'- mer of ethylene or the like. The envelope may be formed "in any suitable manner and that shown in the drawing is formed by placing one edge of the assembledelements' against the median por- "It. is, accordingly, the principal object {the invention to provide a primary cell-with a mag nesium negative electrode having strong current-delivering properties and substantialsheli life in which the electrolytehas a, solutecompo :nent composed of a mixture of magnesium chloride and ,magnesium nit'rate and a solvent com.-

ponent of methanol or a mixture "of "methanol andwater. r Y

Magnesium chloride and magnesium nitrate normally occur in the form of the hexahydrate s MgClzfiI-IzO and Mg (N03) 251-120, and they will for convenience hereinbe called simply the chloride and nitrate, respectively. f

. The single figure of the drawing is a elevation of a cell ofthe present invention.

The physical embodiment shown and described herein is'illustrative, only and the invention is sectional trode 16 of the adjacent cell through the wintionof a strip of the sheet material and'foldin'g: the latter-so thatthe portions thereof on oppo' site sides-of the fold cover the opposite-broad surfacesfiof the assembled elements extend beyond'the edges thereof. The extending-porr tions are then joined together by an adhesive or by heat-sealing to form the joint indicated at 20.. 'O-penings or windows 22 of substantial size are 'provided in the broad portions of the envelope l-8 whichoverlie the electrodes l0 and lfiirespectively. Said openingsarelin alignment with each other and a number of. the cells are adapted to be stacked together in pressure engagement to form a battery with the negative electrode I0 of one cell suitably connected to the positive elecdows 22.

As stated heretofore-the negative electrode l0 is composedof magnesium. The separating memor the like.

her I! may be composed of a suitable bi-bulous material, such as porous paper or pulp. The mix l4 may be composed of a mixture of a suitable oxidizin agent and aconductive agent, such as graphite or other finely divided carbon. Examples of suitable oxidizing agents are manganese dioxide, lead: dioxide, cwpric oxide, silver chloride, the persulfates of sodium and potassium,

dioxide and thermal acetylene black has been found to be very satisfactory. Silver chloride is A mixture of powdered manganese itself conductive and where it is used a separate conductive'agent is not required. The positive electrode [6 may be a flexible sheet, the conductive factor of which is carbon. Such conductive sheet material is well known and may be composed of carbon particles cemented together by a binder, and the composition may, if desired, be reenforcedi.;by--: a;*pprous.fabric sheet lr'as co ton, rayon,- etof 1 As stated heretofore, the solvent component of 10 the electrolyte is methanol or a mixture of meth: .I-.l anol and water, and the solute component .is a mixture of magnesium chloride and magnesium nitrate. The proportions of;thesolute-mixture may be varied, and from about:- 40%2-:to:80%i by ir weight of magnesium chloride, the remainder being magnesium nitrate, has beenfound togive satisfactory improved capacity, and the'pre'ferred proportions are about 40% to 60% by weight ofi f magnesium chloride. A mixture of substantially equal parts of-the said. twocompoundsprovides, ver-y superiorresults. The. compounds mentioned are soluble in methanol, and mixtures of; ,methanol fandiwaterr and formtherewith an..elect rolyticallyactive and conductive;solution.

A specific example ofapell. of thez -ve tionis, one-hav-ingw the physical; structure described 'here- 1 tofore; a negative: electrodeof; magnesium, a depo arizing-i mix composed of a ,mixturepf -powdered." manganese dioxide and thermal. acetylene": go} black, and an electrolyte in whichthesolventand-solute componentsare presentg-in substan tially equahparts by Weight and. the.,solvent:com-'+ ponent ispymethanolvand the.- solutecomponent is a mixtureoi' equal parts.- of; magnesium= chlo rideiand; magnesium nitrate. initial open circuit voltage: of such a "cell is about 2.4 I voltsz- To ShOZlV the Y benefits which are obtained; from thew invention, tests were made, upon batteries? each5made up often series-connected cells .of-the 40" construction given 'instheforegoing example withthe except-ion'thattheproportions of magnesium chloride inat'he 'solute -mixture-were--yaried from; 100%: toll by .weight, theqremainder beingmage nesium-nitrate; Eac-hbattery;.wasiconnectedacom5 tinuously; to; a load' circuit, having: aisresistancer of 115,000fohms. Onegroup of "the --b'a tt,eries; was? subiectedwto dischargewhen they were fresh; that is WithinAB hours after they.had:been.-made;. a" secondasimi-langroup was held im storage; for" 6 months "and was then: placed"; on discharge-:5

The-number ofihours of;continuous service: which eachabatteryl'had deliveredwas noted' whennthez closed:circuit:voltage of the battery had dropped.

to;;l5r-volts: or 1:5-vo1ts-per-cell, which w'asL-con-w sidered'sto 118: a: reasonable; endaipoint." The. table hereinafter? shows thear'esultsxof the tests; Each valueh'given is thepayera'gei of thevresults for" a numbergofrsimilar batteries.

Capacity A: Service to.l.5 Volts";

Electrolyte. Solute Composition. in Ber: 7 cent byWe'ight sequentlyf dissolvedintheelectrolyte and b inf acce The data given in the above table show that the use of a mixture containing about 40% to of magnesium chloride provides a definite advantage over the use of either magnesium chloride or magnesium nitrate alone. The data also show that the optimum proportions are about 40% to 60% of magnesium chloride. They show the siirfirisingphenomen "eater; capacity is =obt'ained with a mixtfire of the compounds over that obtained with either compound alone.

i- As stated hereto-fore, instead of using methanolalone as the solvent, a mixture of water and methanol may be used and an advantage is ob- "tained'in-siich case also from the use of a mix- -ture .ofm'aghesium fchloride and magnesium nitrate. In'-such "c'ell's in which water is present in.; the.electrolyte,. there is included a compound from the group consisting of chromium trioxide and -the "salts of chromic acid which possess at least a slight degree of solubility in water, that is, varying; from sparingly---soluble to extremely, Solublee Such: compound; assists the:- methanol; in: inhibiting; spontaneous corrosion; of the magne-g: sium. Examples ,of.:comp0unds-w;hi0h mayrbe, used: are; chromium-;- tr.ioxi ':le, the -,chroma.tesa of ammonium, barium; calcium; lithium;;potassium,; sodium: and strontium, and =-the dichromatesz. Qfj ammonium, barium; lithium, potassium. and:.-so & clium: Gomp'oundshaving a solubility 'asjow' as 00034. ram; pen -grams ofiwater: are. suitable... barium: chromatebeingrv an; example; of; such Ta: compoundu Chromium:atrioxidewand. the chr o;- mateand; dichromateof. sodiumwhave: been-used; with excellent --resu1ts-.-- As; isifwellknown, chrm;

miumitrioxide is the anhydride-ofi chromic, acid;:.-

and: in therelectrolyte it. exists 'ini. solution in .the waterias chromic acidr- Any onee orsa mixture: of: the compoundsr described may be; used. For-.2 convenience; fsuch. inhibiting :compound willzheree inlbe.calledithe ichromium compound-z 1 The: chromium compound may bejincorp'oratedr in the" cell in any desired manner; as; by: intrmi:

ducing it directly into: the electrolyte; or incor-rsoluble. to i at least 3 a slight degree the water o-fi the' 'electrolyteisolvent, I and the -separating'i member 1-2 i and depolarizing mix I l" are tened With-the electrolyte, ifthe chromium com Do'undis incorporated in these elements it is $11 comes available: at the "surfaceof the-negative electrode.

It is,. therefore, onl y required "that the chroiniumcompound be accessible tothe elecumytauitgt is, that the'v'compound be disposed ss: relation withthefilectrolytef trolytefiin turn;- i sfi' l iii deu t bf. chromium ompound I eus islnot criticaL Only aQSmalla is "requiredj'and an excessive amount should bei avoided sincethis results in a-wasteyqf; the com pound: and may-interfere. with the 1' proper opera tion of the cell. '-Am0.l1nts 10f; chromium. com-L:

- poundwhich have-Jbeen-iused with successsarea about .01% to 5.0%,-' in termsio'f: CrOa'base the weight of the water in the solvent co nent, bywh'ich is es-mm not include-the combin Jul-w,

v e mp0- efree waterand does gerw we present, such as the water of hydration of the solute.

A specific example of a cell of the last described character is one similar to the example described heretofore with the difierence that the solvent component of the electrolyte is a mixture of equal parts by weight ofmethanol andwater and the electrolyte contains sodium dichromate in the amount of .06% in terms of C1 03 based on the amount of water in the solvent.

To show the benefits obtained from the mixture of magnesium chloride and magnesium nitrate when water is present in the solvent, data are given in Table 2 hereinafter for batteries of a construction similar to that of the foregoing example in which the solvent component of the cells was a mixture of equal parts of water and methanol and the solute component was various mixtures of magnesium chloride and magnesium nitrate, the solute being present in an amount by weight equal to that of the solvent. In these batteries sodium dichromate was incorporated in the electrolyte containing CIOs in an amount equal to approximately .06% of the weight of the water. The conditions of the tests were similar to those described heretofore. In compiling the data, tests were made on a group of batteries which were fresh and also on a group which had been aged for three months before discharge was commenced. Each value given in the table is the average of the results for a number of similar batteries.

Table 2 Capacity in Hours Service to 1.5 Volts Solute Composition Percent by Weight Per Cell End Point MgClzfiHiO Mg(N :)2- 2 Fresh rig in The data show that definitely superior performance is obtained when a mixture of the solute compounds is used containing about 50% to 75 of magnesium chloride, over that obtained when either compound is used alone. Many tests in addition to those listed in Table 2 were made on batteries having various proportions of the solute ingredients and of the solvent ingredients, and an advantage was obtained with the solute mixture when the amount of magnesium chloride varied from about 40% to 80% of the combined weight of the two compounds with methanol alone as the solvent and also when water is present in an amount up to about 70% of the combined weight of the methanol and water. If water is solute mixture are about to 60% by weight of magnesium chloride.

What is claimed is:

1. In a primary cell having a positive electrode and a magnesium negative electrode, an electrolyte in contact with said electrodes having a solvent component comprising essentially methanol and a solute component comprising essentially a mixture of magnesium chloride and magnesium nitrate.

2. In a primary cell having a positive electrode and a magnesium negative electrode, an electrolyte in contact with said electrodes having a solvent component comprising essentially methanol and a solute component comprising essentially a mixture of magnesium chloride and magnesium nitrate in which the amount of magnesium chloride is about 40% to 80% of theweight of the mixture.

3. a In a primary cell having a positive electrode and a magnesium negative electrode, an electrolyte in contact with said electrodes having a solvent component comprising essentially methanol and a solute component comprising essentially a mixture of magnesium chloride and magnesium nitrate in which the amount of magnesium chloride is about 40% to 60% of the weight of the mixture.

4. In a primary cell having a positive electrode and a magnesium negative electrode, an electrolyte in contact with said electrodes having a solvent component comprising essentially a mixture of methanol and water containing up to by weight of water, and a solute component comprising essentially a mixture of magnesium chloride and magnesium nitrate in which the amount of magnesium chloride is about 40% to of the weight of the mixture, and a compound in access relation with said electrolyte from the group consisting of chromic acid and the salts of chromic acid having at least a slight degree of solubility in water, said compound being present in an amount suflicient to inhibit spontaneous corrosion of said magnesium electrode.

IVAN C. BLAKE.

REFERENCES CITED The following references are of record in the I file of this patent: v

UNITED STATES PATENTS 

1. IN A PRIMARY CELL HAVING A POSITIVE ELECTRODE AND A MAGNESIUM NEGATIVE ELECTRODE, AN ELECTROLYTE IN CONTACT WITH SAID ELECTRODES HAVING A SOLVENT COMPONENT COMPRISING ESSENTIALLY METHANOL AND A SOLUTE COMPONENT COMPRISING ESSENTIALLY A MIXTURE OF MAGNESIUM CHLORIDE AND MAGNESIUM NITRATE. 